Sensing the ortho Positions in C6Cl6 and C6H4Cl2 from Cl2 Formation upon Molecular Reduction

Sarvesh Kumar, José Romero, Michael Probst, Thana Maihom, Gustavo García, Paulo Limão-Vieira

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The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl2. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using ortho-, meta- and para-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl2 formation can only occur in 1,2-C6H4Cl2, where the two closest C–Cl bonds are cleaved while the chlorine atoms are brought together within the ring framework due to excess energy dissipation. These results show that a strong coupling between electronic and C–Cl bending motion is responsible for a positional isomeric effect, where molecular recognition is a determining factor in chlorine anion formation.

Original languageEnglish
Article number4820
Number of pages13
Issue number15
Publication statusPublished - 27 Jul 2022


  • charge transfer
  • collision induced dissociation
  • dichlorobenzene
  • geometric effect
  • hexachlorobenzene


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